Catalytic process for the manufacture of polyamides from diamines and diamides

ABSTRACT

Nylon-type polyamides are produced from a diamine and a diamide in contact with an oxygenated phosphorus compound catalyst. For example, high quality nylon-6,6 is manufactured by contacting hexamethylenediamine and adipamide in water with an oxygenated phosphorus compound at an elevated temperature and pressure.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to polyamides. In one aspect, the invention relates to a process for manufacturing polyamides from α,ω-diamine and an α,ω-diamide while in another aspect, the invention relates to a process utilizing an oxygenated phosphorus compound as a catalyst. In still another aspect, the invention relates to an improved process for manufacturing nylon-6,6 from hexamethylenediamine and adipamide utilizing a catalyst system composed of an oxygenated phosphorus compound.

2. Description of the Prior Art

It is known in the art that commercially available nylons may be prepared by polymerization of various monomers and combinations of monomers. For example, various nylons may be prepared from the polymerization of diamines with dicarboxylic acids, the polymerization of dinitriles with diamines in the presence of water, the polymerization of aminonitriles in the presence of water, or the polymerization of lactams.

In part, the instant invention deals with nylons resulting from the polymerization from diamines and diamides. Very few references suggest the polymerization of these two monomer types. For example, U.S. Pat. No. 3,900,450 teaches a process for polymerizing amino acids, diamines, dibasic carboxylic acids and other amide forming derivatives in which diamides are specifically included.

In part, the instant invention also relates to the use of an oxygenated phosphorus compound as a polymerization catalyst. Recently Hoffmann et al., U.S. Pat. No. 4,436,898 disclosed an improved method for preparing a high molecular weight polyamide from a dinitrile, diamine and water by conducting the polymerization in the presence of an oxygenated phosphorus compound, such as phosphoric acid, or an ammonium salt or an ammonium alkyl salt of the acid. Also recently, Coffey et al., U.S. Application Ser. No. 540,596, now U.S. Pat. No. 4,490,521, disclosed a method for the improvement of resin thermal stability through the use of metal salts of oxyphosphorus acids, such as disodium phosphite, as the catalyst.

Lastly, the instant invention relates to the production of nylon-6,6 from hexamethylenediamine and adipamide. Commercially nylon-6,6 is produced from hexamethylenediamine and adipic acid. The present invention offers an alternative to the adipic acid route in preparing this most useful polymer.

SUMMARY

Nylon-type polyamides suitable for fibers, plastics, films and molding compounds are produced in a process comprising contacting an α,ω-diamine, and an α,ω-diamide in the presence of an oxygenated phosphorus compound catalyst. In one embodiment, nylon-6,6 is produced by contacting hexamethylenediamine and adipamide in water and in the presence of the oxygenated phosphorus compound catalyst.

DETAILED DESCRIPTION OF THE INVENTION

Monomers:

The α,ω-diamines here used are of the formula

    R'HN--R--NHR'                                              (I)

where R is a divalent organic radical and each R' is independently hydrogen or a univalent organic radical. R can be a divalent aliphatic, alicyclic or aromatic radical and these radicals can bear one or more inert substituents. Similarly, each R' can be independently a hydrogen or a univalent aliphatic, alicyclic or aromatic radical and each one of these radicals can also bear one or more inert substituents. By the term "inert" is meant that the substituent is essentially nonreactive with the reactants, catalysts and products of the process under process conditions. Typically, R is a divalent C₁ -C₂₀ aliphatic radical, a divalent C₅ -C₁₈ alicyclic radical or a divalent benzene radical and preferably R is a C₂ -C₈ straight chain alkylene radical. Typically, R' is hydrogen or a C₁ -C₂₀ aliphatic radical, C₅ -C₇ alicyclic or a phenyl radical. Preferably, R' is hydrogen or a C₁ -C₄ alkyl radical. Representative diamines include tetramethylene diamine, hexamethylenediamine, p-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 4,4'-diaminodicyclohexyl sulfide, 4,4'-diaminodicyclohexyl sulfone, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, m-xylylenediamine, 1,4-dimethyleneamino-1-phenyl-1,2,3,4-tetrahydronaphthalene and the like. Hexamethylenediamine is an especially preferred diamine.

The diamides here used are of the formula ##STR1## where R is as previously defined. Representative diamides include malonamide, succinamide, glutaramide, adipamide, terephthalamide and isophthalamide. Adipamide is an especially preferred diamide.

The instant invention is substantially aimed at the production of nylon-type polyamides from diamines and diamides. However, other nylon-type polyamides can also be prepared by the instant process by the polymerization of diamines, diamides and other polyamide forming compounds. Representatives of other polyamide forming compounds are lactams, such as caprolactam, valerolactam, undecalactam; amino carboxylic acids; aliphatic and aromatic dicarboxylic acids, such as adipic acid, succinic acid, sebacic acid, isophthalic acid and terephthalic acid; and aliphatic and aromatic dinitriles, such as glutaronitrile, succinonitrile, adiponitrile, suberonitrile, sebaconitrile, 1,10-decane dinitrile, methyl glutaronitrile, α-methylene glutaronitrile and 1,4-dicyano-1-phenyl-1,2,3,4-tetrahydronaphthalene.

The Catalyst

The oxygenated phosphorus compounds suitable for use as catalysts in the invention include phosphorous acid; phosphonic acid, alkyl and aryl substituted phosphonic acid, hypophosphorous acid, alkyl, aryl and alkyl/aryl substituted phosphinic acid; and phosphoric acid; as well as the alkyl, aryl and alkyl/aryl esters, metal salts, ammonium salts, and ammonium alkyl salts of these various phosphorus containing acids. As used herein, "alkyl/aryl" refers to those combinations where there is more than one organic substituent. In the substituted acids, the alkyl or aryl group replaced the hydrogen connected directly to the phosphorus atom. The esters are formed conventionally with the alkyl or aryl group replacing the hydrogen of an --OH group comprising the acid. To clarify the nomenclature, the names of the acids are identified with the structural formulas as follows: ##STR2## where R'" is an alkyl or aryl or alkyl/aryl group and R^(IV) is hydrogen or an alkyl or aryl group. In common usage. phosphonic acid shares the name phosphorous acid.

Preferred oxygenated phosphorus compounds are phosphorous acid, phosphoric acid, and the sodium, lithium or sodium/lithium dibasic salts of phosphorous or phosphoric acids. These salts may be added initially or generated in situ by the addition of NaOH or LiOH ot a reaction mixture already containing the oxyphosphorus acid or a monobasic salt thereof at a time late in the reaction cycle.

Equally preferred oxygenated phosphorus compounds are the salts of phosphorous acid, phosphonic acid, hypophosphorous acid, phosphinic and phosphoric acid which are formed by combining any cation with any of these acids. Preferred cations for this purpose are univalent metals and ammonium. More preferred are the neutral salts of these acids, such as the dibasic salts of alkali metals such as the sodium, lithium or sodium/lithium dibasic salts described in the preceding paragraph. In general, the salts are preferred catalysts because they yield a polyamide exhibiting a high onset decomposition temperature.

Sufficient catalyst is employed to promote the polymerization of the diamine and diamide. A typical amount of catalyst is between 0.0001 and 1 weight percent, based upon the total weight of the diamine, diamide, and water. Catalyst levels of about 0.001 to about 1 weight percent are preferred.

The manner in which the catalyst is added to the monomers can vary, e.g. addition of each component separately to a mixture of monomers or added as a mixture to one of the monomers prior to admixture with the other monomer.

Process Parameters

High molecular weight, linear polyamides are prepared by forming a reaction mixture of the diamine, diamide, water and catalyst. This reaction mixture can be formed by any one of a number of different methods. One method is the gradual addition, either continuously or incrementally, of the diamine to the diamide over the course of the polymerization. Typically, in this method less than 50 mole percent of the diamine, preferably less than 5 mole percent, is admixed with the diamide with the remainder of the diamine added gradually over the course of polymerization. Another method and one preferred due to its simplicity of operation is a batch addition of all reactants at the commencement of the reaction.

The reaction itself is preferably conducted in a batch mode. However, the reaction can also be conducted in a continuous mode, i.e. continual addition of the reactants with concomitant removal of product, if desired. An example of a continuous mode process is the use of a cascade reactor arrangement.

Thoretically, water is not necessary to the process as reactant, but in practice it has been found that it is beneficial to the production of high molecular weight polyamides. Consequently, water is typically employed in the reaction mixture during the polymerization. Since the water will have to be removed from the reaction product at the end of the polymerization, preferably the amount of water is kept to a minimum (20 weight percent or less) to facilitae ultimate removal. Moreover, the less water present during the polymerization generally means the less energy needed for the process and consequently, less expensive process equipment can be employed. The manner in which the water is initially introduced into the reaction mixture is not important to the practice of this invention and it can thus be either added alone or in combination with the diamine or diamide. Additionally, other solvents or diluents may be used in the process as an alternative to water.

Ammonia is a byproduct of the reaction of the diamine and diamide. As a consequence, ammonia is constantly being generated within the reaction mixture but it typically enters the vapor phase and is preferably continuously removed from reaction zone (e.g. released through a pressure relief valve on the reaction vessel). The concentration of ammonia in the reaction mixture (which is a liquid) can vary from threshold detection limits up to about 5 weight percent of the total weight of the reaction mixture. Preferably, the concentration of ammonia in the liquid reaction mixture does not exceed 1 weight percent and more preferably, is kept as low as possible.

In one embodiment of this invention, high quality nylon-6,6 resin is prepared from hexamethylenediamine and adipamide in water by continuously removing substantially all of the ammonia generated during the polymerization but while retaining all of the water. The water is eventually removed from the reaction system after low molecular weight polyamides are formed.

The polymerization of a diamine and a diamide to form a high molecular weight, linear polyamide is best conducted over a temperature/pressure profile that varies over the course of the polymerization. The temperature/pressure profile will, of course, vary with the specific reactants employed as well as with such factors as the nature and amount of catalysts, mode of operation (batch versus continuous), configuration of the reaction vessel, etc. For the manufacture of nylon-6,6 fro hexamethylenediamine and adipamide in water, a temperature/pressure profile comprising at least two stages is typically employed, both preferably conducted in the absence of air (O₂). During the first stage of the polymerization, the temperature is maintained at 180°-300° C., preferably 200°-270° C., under autogenous pressure (typically about 200 to about 800 psi absolute) for a period of time sufficient to form low molecular weight polyamides, e.g. polyamides having a weight average molecular weight of less than about 10,000, generally less than about 5,000 as measured by intrinsic viscosity. Ammonia is removed from the reaction vessel while maintaining the water concentration at a level sufficient to aid polymerication, typically in excess of 14 weight percent. At the completion of the first stage (which is the start of the second stage), the pressure is gradually reduced to atmospheric or subatmospheric pressure and the temperature is gradually increased, preferably to between about 260°-295° C. During this second stage, relatively low molecular weight polyamides are combined to form the high molecular weight polyamides that constitute the final product of the process. The second stage is typically concluded with a sweep or purge of the reaction vessel with a flow of inert gas, such as nitrogen.

In one embodiment of this invention, the molecular weight of the polyamide can be increased by performing the polymerization at a temperature just below the lowest temperature at which either the catalyst, monomers or final polyamide begin to degrade.

Although the polymerization is initially conducted at autogenous pressure with a later reduction to atmospheric or subatmospheric pressure, the process can be conducted at constant pressure by applying an inert gas pressure to the system and adjusting this pressure as the reaction proceeds. The pressure can be maintained with a gaseous reactant or a gas inert to the reaction or some combination of the two. However, since the reaction itself is conducted in the liquid phase, the presence of a gaseous reactant is for the purpose of maintaining reaction pressure, not for participating in the polymerization.

The Polyamide

The polyamides produced by this invention are solid high molecular weight products having a nylon structure, i.e. amide linkages (--CONH--) as an integral part of the polymer backbone, as opposed to polyacrylamides which have an essentially all carbon backbone. These polyamides can be used in any application calling for the use of a nylon-type polymer. For example, these polyamides can be used as fibers, plastics, films and molding compounds.

As earlier disclosed, when a salt of one of the several phosphorus containing acids is used as a catalyst, the polyamides are characterized by relatively high onset decomposition temperature (ODT). This property is directly related to the stability of the polymer, the higher the ODT, the more thermally stable the polyamide. Typically, the polyamides produced by this invention have an ODT higher than about 330° C. which is of economic value in the marketplace since such polyamides will undergo less thermal degradation during processing. For example, fiber spinning apparatus will require less down time for cleaning when processing a relatively high ODT polyamide than when processing a lower ODT polyamide. In addition, themal gravimetric analysis (TGA) shows that the polyamides made by this invention have relatively low weight loss.

The polyamides produced by this invention are believed to contain few, if any, defect structures. A defect structure is simply a branch or side chain attached to the polymer backbone which is formed when a monomer, oligomer or low molecular weight polymer attaches to the polymer backbone as a pendent substituent rather than as an integral part of the backbone itself. Although these defect structures may be present in relatively low concentrations, even in extremely low concentrations, even parts per million, their presence can confer undesirable thermal instability to the polyamide. The practice of this invention reduces the formation of defect structures to the polyamide to a minimum.

This invention is particularly well adapted to manufacturing high quality nylon-6,6 polymer from hexamethylenediamine and adipamide, in contact with the catalyst and water. However, this invention is also useful for the manufacture of nylon-4,4; nylon-4,6; and nylon-6,4 (from the appropriate diamines and diamides).

The following examples are illustrative of various embodiments of this invention. Unless noted to the contrary, all parts and percentages are by weight.

SPECIFIC EMBODIMENTS EXAMPLES 1-19:

All examples were run in a Parr autoclave (450 ml) equipped with an anchor agitator. The reactor was charged with adipamide (72.09 g, 0.5 moles), hexamethylenediamine (58.15 g, 0.5004 moles), water (33.51 g, 1.86 moles) and catalyst. The reactor was then purged with nitrogen, sealed and connected to a back-pressure regulator adjusted to 750 psi absolute. The reaction mixture was then heated with stirring to 260° C. The reaction temperature/pressure profile was as follows: Five minutes at 260° C. and 750 psi, 15 minutes at 260°-280° C. while venting to atmospheric pressure, and then 10 minutes at 260°-280° C. with the reactor swept with nitrogen. The reactor was then cooled to room temperature under a positive nitrogen pressure. Nylon-6,6 polymer was recovered from the reactor and ground to a size such that it would pass through a ten mesh (U.S. Standard) screen. Melting point and onset decomposition temperature (ODT) was measured by differential scanning calorimetry (DSC). Weight loss was measured by thermal gravimetric analysis (TGA). Intrinsic viscosity was determined in formic acid (90 weight percent) at 25° C. Bulk viscosity was the time required for 0.415 g of polymer dissolved in 2 ml of 90 percent formic acid to traverse 0.8 ml in a 1 ml pipette at room temperature.

Identification of catalysts and the results are reported in Table I.

EXAMPLES 20-21:

Polyamides (90% Nylon-6,6/10% Nylon-6) were prepared from adipamide, hexamethylenediamine and ε-caprolactam using the same procedure described for Examples 1-19. The concentrations of the reactants for Examples 20-21 are as follows: adipamide (64.88 g, 0.45 moles), hexamethylenediamine (52.34 g, 0.4504 moles), ε-caprolactam (11.32 g, 0.1 mole) and water (33.51 g, 1.86 moles).

Identification of the catalysts and the results are reported in Table II.

                                      TABLE I                                      __________________________________________________________________________     NYLON-6,6 PREPARATION FROM ADIPAMIDE AND HEXAMETHYLENEDIAMINE                                 Catalyst                                                                             Bulk  Intrinsic                                                                           TGA WT                                                                               DSC Onset                                                                              DSC                              Example        Conc. Viscosity                                                                            Viscosity                                                                           Loss (%)                                                                             Decomp. Temp                                                                           Melting                          Number                                                                              Catalyst  (Mole %)                                                                             (Seconds)                                                                            (DL/G)                                                                              325-390° C.                                                                   Degrees C.                                                                             Point (°C.)               __________________________________________________________________________     1    none      none  11.97 0.74 2.2   360     264                              2    H.sub.3 PO.sub.3                                                                         0.1460                                                                               114.71                                                                               2.17 9.1   305     262                              3    Na.sub.2 HPO.sub.3                                                                       0.1460                                                                               68.43 1.49 1.6   355     265                              4    Na.sub.2 HPO.sub.3                                                                       0.0146                                                                               42.00 1.53 1.1   345     263                              5    NaLiHPO.sub.3                                                                            0.1460                                                                               24.75 1.20 1.4   340     263                              6    H.sub.3 PO.sub.4                                                                         0.1460                                                                               82.85 2.03 9.0   340     262                              7    NaH.sub.2 PO.sub.4                                                                       0.1460                                                                               99.02 2.08 5.6   345     263                              8    Na.sub.2 HPO.sub.4                                                                       0.1460                                                                               51.78 1.61 2.0   350     264                              9    Na.sub.3 PO.sub.4                                                                        0.1460                                                                               16.20 0.94 7.0   340     261                              10   CaHPO.sub.4                                                                              0.1460                                                                               52.76 1.65 7.0   305     261                              11   AlPO.sub.4                                                                               0.1460                                                                               66.87 1.77 3.3   325     261                              12   H.sub.3 PO.sub.2                                                                         0.1460                                                                               80.37 1.93 8.0   305     262                              13   Mn(H.sub.2 PO.sub.2).sub.2                                                               0.1460                                                                               88.14 2.05 7.7   305     258                              14   C.sub.6 H.sub.5 P(O)(OH)H                                                                0.1460                                                                               45.62 1.49 8.8   340     264                              15   C.sub.6 H.sub.5 P(O)(ONa)H                                                               0.1460                                                                               22.53 1.12 2.6   335     262                              16   C.sub.6 H.sub.5 P(O)(OH).sub.2                                                           0.1460                                                                               38.00 1.41 6.7   340     264                              17   (CH.sub.3 O).sub.3 P(O)                                                                  0.1460                                                                               53.24 1.65 8.8   310     262                              18   (CH.sub.3 O).sub.2 P(O)CH.sub.3                                                          0.1460                                                                               60.46 1.71 5.6   325     262                              19   (C.sub.8 H.sub.17 O).sub.2 P(O)H                                                         0.1460                                                                               70.53 1.92 6.4   310     260                              __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________     PREPARATION OF 90/10 NYLON-6,6 FROM ADIPAMIDE,                                 CAPROLACTAMNEDIAMINE AND                                                                  Catalyst                                                                             Bulk  Intrinsic                                                                           TGA WT                                                                               DSC Onset                                                                              DSC                                  Example    Conc. Viscosity                                                                            Viscosity                                                                           Loss (%)                                                                             Decomp. Temp                                                                           Melting                              Number                                                                              Catalyst                                                                             (Mole %)                                                                             (Seconds)                                                                            (DL/G)                                                                              325-390° C.                                                                   Degrees C.                                                                             Point (°C.)                   __________________________________________________________________________     20   none  none  20.28 1.12 1.9   360     248                                  21   Na.sub.2 HPO.sub.3                                                                   0.1460                                                                               29.14 1.32 1.4   360     249                                  __________________________________________________________________________

Since viscosity is proportional to molecular weight, Table I and Table II both illustrate that polyamides produced from diamines and diamides using the catalytic process of the instant invention have greater viscosities and consequently greater molecular weight than polyamides produced using an identical process without a catalyst.

Although the invention has been described in considerable detail through the preceding examples, these examples are for the purpose of illustration only and one skilled in the art will understand that variations and modifications can be made without departing from the spirit and scope of the invention. 

The claimed invention is:
 1. A process for the manufacture of a solid polyamide comprising contacting an α,ω-diamine, an α,ω-diamide and an oxygenated phosphorus compound catalyst at an elevated temperature and pressure.
 2. The process of claim 1, wherein the α,ω-diamine, the α,ω-diamide and the oxygenated phosphorus compound catalyst are contacted in water.
 3. The process of claim 1 where the oxygenated phosphorus compound is selected from the group consisting of phosphorous acid; phosphonic acid; alkyl or aryl substituted phosphonic acid; hypophosphorous acid, alkyl, aryl or alkyl/aryl substituted phosphinic acid; phosphoric acid; the alkyl, aryl, or alkyl/aryl esters of phosphorous acid, phosphonic acid, phosphinic acid, phosphoric acid or alkyl or aryl substituted phosphonic or phosphinic acid; and the metal salts, ammonium salts or ammonium alkyl salts of phosphorous acid, phosphonic acid, phosphinic acid, phosphoric acid or alkyl or aryl substituted phosphonic or phosphinic acid.
 4. The process of claim 3 where the oxygenated phosphorus compound is a metal salt of an oxygenated phosphorus compound.
 5. The process of claim 4 where the metal salt of an oxygenated phosphorus compound is an alkali metal salt of an oxygenated phosphorus compound.
 6. The process of claim 3 where the metal salt of an oxygenated phosphorus compound is an alkali metal salt of at least one of phosphorous acid or phosphoric acid.
 7. The process of claim 6 where the metal salt of an oxygenated phosphorus compound is selected from the group consisting of the sodium and lithium salts of at least one of phosphorous acid and phosphoric acid.
 8. The process of claim 7 where the metal salt of an oxygenated phosphorus compound is the disodium salt of at least one of phosphorous acid or phosphoric acid.
 9. The process of claim 6 where the metal salt of an oxygenated phosphorus compound is the dilithium salt of at least one of phosphorous acid or phosphoric acid.
 10. The process of claim 6 where the metal salt of an oxygenated phosphorus compound is the lithium sodium salt of at least one of phosphorous acid or phosphoric acid.
 11. The process of claim 1 where the catalyst is present in an amount between about 0.0001 to about 1 weight percent based upon the total weight of the diamine, diamide and water.
 12. The process of claim 1 where the diamine is of the formula

    R'HN--R--NHR'                                              (I)

and where the diamide is of the formula ##STR3## where each R is independently a divalent organic radical and each R' is independently hydrogen or a univalent organic radical.
 13. The process of claim 12 where R is a divalent C₁ -C₂₀ aliphatic, divalent C₅ -C₁₈ alicyclic or divalent benzene radical and each R' is independently hydrogen, a univalent C₁ -C₂₀ aliphatic, univalent C₅ -C₇ alicyclic or a phenyl radical.
 14. The process of claim 13 where R is a C₂ -C₈ straight chain alkalene radical and R' is hydrogen or a C₁ -C₄ alkyl radical.
 15. The process of claim 14 where the diamine is hexamethylene diamine and the diamide is adipamide.
 16. The process of claim 1 wherein a α,ω-diamine and the α,ω-diamide are polymerized with other polyamide forming compounds selected from the group consisting of lactams, amino-carboxylic acids, aliphatic and aromatic dicarboxylic acids and aliphatic and aromatic dinitriles.
 17. The process of claim 14 where the α,ω-diamine and the α,ω-diamide are polymerized with ε-caprolactam. 